We report a facile, green, and biomimetic reduction route coupled with the synthesis and biomolecular-based well-defined self-assembly of gold nanoparticles (AuNPs), without using any organic solvents or any toxic reducing or capping agents. To demonstrate the potential use of pear phytochemicals for the materialization ofAuNPs, we propose that the available biomolecules appending on the AuNPs surface and subsequently observed their importance in assembly designs. The spatial array of AuNPs was investigated precisely by using a high-resolution transmission electron microscopy. This method offered biomolecular capping of the AuNPs during and after synthesis and thus provides a promising alternative for nanosurface engineering. The peptide and other biomolecule-based coatings on the AuNPs are applicable for their stability and healthy capping. The hybrid "biomolecular-inorganic" system will be suitable for safe application in medical and diagnostic fields.